Patent GB-739266-A (GB)
Title: Improvements relating to the preparation of non ionic surface active agents
IPC: C09K23/00
Filed: 1952-05-22
Abstract: Cotton fabrics are bleached with hypochlorites with aid of non-ionic surface-active agents having the general formula <FORM:0739266/IV (c)/1> wherein Y is the residue of an organic compound YH, and comprises a monovalent unsubstituted or substituted aliphatic and/or aromatic group and H is a single hydrogen atom and the only hydrogen atom in YH capable of reacting with an a ,b -alkylene oxide; R1, R2, R3 and R4 are hydrogen or aliphatic or aromatic radicals, at least one being other than hydrogen, which radicals may be substituted with groups which do not contain a hydrogen atom capable of reacting with an a ,b -alkylene oxide, or R1 and R2 and R3 and R4 may be joined together to form carbocyclic rings; n is a number (as determined by hydroxyl number) which is such that when the total carbon atoms in R1, R2, R3 and R4 is 1 then n is at least 6.4 and when said total number of carbon atoms is 2 or more then n is at least 3; and X is a polyoxyalkylene chain in which the individual oxyalkylene groups conform to the formula <FORM:0739266/IV (c)/2> wherein R5, R6, R7 and R8 are selected from hydrogen, -CH2OH and <FORM:0739266/IV (c)/3> the number of oxyalkylene units in X being such that X constitutes 20-95 per cent by weight of the surface-active agents.  The preparation of these agents is described (see Group IV (b)).ALSO:The invention relates to non-ionic surface-active agents having the general formula <FORM:0739266/IV (a)/1> wherein Y is the residue of an organic compound YH, and comprises a monovalent unsubstituted or substituted aliphatic and/or aromatic group and H is a single hydrogen atom and the only hydrogen atom in YH capable of reacting with an a ,b -alkylene oxide; R1, R2, R3\h and R4 are hydrogen or aliphatic or aromatic radicals, at least one being other than hydrogen, which radicals may be substituted with groups which do not contain a hydrogen atom capable of reacting with an a ,b -alkylene oxide, or R1 and R2 and R3 and R4 may be joined together to form carbo-cyclic rings; n is a number (as determined by hydroxyl number) which is such that when the total carbon atoms in R1, R2, R3 and R4 is 1 then n is at least 6.4 and when said total number of carbon atoms is 2 or more then n is at least 3; and X is a poly oxyalkylene chain in which the individual oxyalkylene groups conform to the formula <FORM:0739266/IV (a)/2> wherein R5, R6, R7 and R8 are selected from hydrogen, -CH2OH and <FORM:0739266/IV (a)/3> , the number of oxyalkylene units in X being such that X constitutes 20-95 per cent by weight of the surface-active agents.  The products may be prepared by reacting the compounds YH with appropriate amounts of one or more alkylene oxides having the formula <FORM:0739266/IV (a)/4> normally at elevated temperature and pressure in the presence of an alkaline catalyst, e.g. sodium hydroxide, sodium alkoxide or a quaternary ammonium base, and then reacting the product with one or more alkylene oxides having the formula <FORM:0739266/IV (a)/5> in amounts sufficient to provide the value of X, the R's having the above defined meanings.  The oxides may be replaced by the corresponding polyoxy alkylene glycols. The first mentioned class of alkylene oxide includes, for example, 1 : 2-propylene oxide, 1 : 2 - butylene oxide, 2 : 3 - butylene oxide, isobutylene oxide, amylene oxide, cyclohexene oxide, octene oxide, styrene oxide and butadiene oxide and mixtures of propylene and butylene oxides and amylene and cyclohexene oxides.  The second type of alkylene oxide is exemplified by ethylene oxide.  The organic compounds YH include monofunctional alcohols, phenols, carboxylic acids, secondary amines, N-substituted amides including sulphonamides and mercaptans and they may contain such substituents as Cl, Br, I, -NO3, -NO2 and the alkoxy radical.  Compounds mentioned in addition to those referred to below, include tertiary butanol, 2-chlorethanol, methyl ether of diethylene glycol, chlorphenol, cresols, naphthols, formic acid, chloracetic acids, pentanoic acid, benzoic acid, naphthoic acid, dimethylamine, N-methyl steraylamine, phenyl b -naphthylamine, N-methyl formamide, N-ethyl benzoic acid amide, N-methyl ethane sulphonamide, N-phenyl toluene sulphonamide, methyl mercaptan, iso- and tert.-butyl mercaptans, thiophenol and thionaphthols. In examples (15) 1 : 2-propylene oxide is fed gradually into a heated autoclave containing n-propanol and sodium hydroxide catalyst until an intermediate product is formed having a value for n of 11.7 whereupon this product is similarly reacted with ethylene oxide until the resulting product contains 50 per cent by weight of poly oxyethylene chain; (16) n-butanol is similarly reacted with propylene oxide, yielding an intermediate product, having a value for n of 9.8, which is reacted with ethylene oxide to provide 50 per cent poly-oxyethylene groups in the final product; (17) as in 15, the final product containing 41 per cent polyoxyethylene; (18) n-butanol is similarly reacted with cyclohexene to yield a product containing 2-oxycyclohexene groups in a chain which product is further reacted with cyclohexene and then with ethylene oxide; (19) phenol is similarly reacted with styrene oxide in two stages yielding an intermediate, having a value for n of 3.66, which is reacted with ethylene oxide to yield a product containing 72 per cent poly-oxyethylene; (20) n-propanol is reacted with various proportions of propylene oxide yielding intermediates, having values for n of from 6.4 to 11.7, which are reacted with ethylene oxide yielding products containing 38-61 per cent polyoxyethylene whose detergencies are compared; similar compounds are prepared from n-propanol and 1 : 2-butylene oxide and ethylene oxide, n being from 3.1 to 6.1 and the poly-oxyethylene contents 61-66 per cent; (21) methanol, n-propanol, n-butanol, n-hexanol, lauryl alcohol, phenol, N-ethyl benzene sulphonamide, oleic acid, N-phenyl benzene sulphonamide, nonyl phenol and crude tall oil acid are reacted separately with 1 : 2-propylene oxide as above yielding intermediate having n = 6.4 to 12.6 which are reacted with ethylene oxide to form compounds containing 41-80 per cent poly-oxyethylene and their cleansing properties are compared. The production and properties of many other like compounds from n-butanol and 1 : 2-propylene oxide and n-propanol and 1 : 2-butylene oxide with final oxyethylation, are described.  The surface-active agents may be used as plasticizers in vinyl resins, phenolic resins and synthetic rubbers.ALSO:The invention relates to non-ionic surface-active agents having the general formula <FORM:0739266/IV (b)/1> wherein Y is the residue of an organic compound YH, and comprises a monovalent unsubstituted or substituted aliphatic and/or aromatic group and H is a single hydrogen atom and the only hydrogen atom in YH capable of reacting with an a ,b -alkylene oxide; R1, R2, R3\h and R4 are hydrogen or aliphatic or aromatic radicals, at least one being other than hydrogen, which radicals may be substituted with groups which do not contain a hydrogen atom capable of reacting with an a ,b -alkylene oxide, or R1 and R2 and R3 and R4 may be joined together to form carbo-cyclic rings; n is a number (as determined by hydroxyl number) which is such that when the total carbon atoms in R1, R2, R3 and R4 is 1 then n is at least 6.4 and when said total number of carbon atoms is 2 or more then n is at least 3; and X is a poly-oxyalkylene chain in which the individual oxyalkylene groups conform to the formula <FORM:0739266/IV (b)/2> wherein R5, R6, R7 and R8 are selected from hydrogen, -CH2OH and <FORM:0739266/IV (b)/3> , the number of oxyalkylene units in X being such that X constitutes 20-95 per cent by weight of the surface-active agents.  The products may be prepared by reacting the compounds YH with appropriate amounts of one or more alkylene oxides having the formula <FORM:0739266/IV (b)/4> normally at elevated temperature and pressure in the presence of an alkaline catalyst, e.g. sodium hydroxide, sodium alkoxide or a quaternary ammonium base, and then reacting the product with one or more alkylene oxides having the formula <FORM:0739266/IV (b)/5> in amounts sufficient to provide the value of X, the R's having the above-defined meanings.  The oxides may be replaced by the corresponding poly-oxalkylene glycols.  The first-mentioned class of alkylene oxide includes, for example, 1 : 2-propylene oxide, 1 : 2-butylene oxide, 2 : 3-butylene oxide, isobutylene oxide, amylene oxide, cyclohexene oxide, octene oxide, styrene oxide and butadiene oxide and mixtures of propylene and butylene oxides and amylene and cyclohexene oxides.  The second type of alkylene oxide is exemplified by ethylene oxide.  The organic compounds YH include monofunctional alcohols, phenols, carboxylic acids, secondary amines, N-substituted amides including sulphonamides and mercaptans and they may contain such substituents as Cl, Br, I, -NO3, -NO2 and the alkoxy radical. Compounds mentioned in addition to those referred to below, include tertiary butanol, 2-chlorethanol, methyl ether of diethylene glycol, chlorphenol, cresols, naphthols, formic acid, chloracetic acids, pentanoic acid, benzoic acid, naphthoic acid, dimethylamine, N-methyl stearylamine, phenyl b -naphthylamine, N-methyl formamide, N-ethyl benzoic acid amide, N - methyl ethane sulphonamide, N - phenyl toluene sulphonamide, methyl mercaptan, iso and tert.-butyl mercaptans, thiophenol and thionaphthols.  In examples (15) 1 : 2-propylene oxide is fed gradually into a heated autoclave containing n-propanol and sodium hydroxide catalyst until an intermediate product is formed having a value for n of 11.7 whereupon this product is similarly reacted with ethylene oxide until the resulting product contains 50 per cent by weight of poly-oxyethylene chain; (16) n-butanol is similarly reacted with propylene oxid